Nano-fiber membranes hold great promise for use in filtration applications. In this study, a photocatalytic polyvinyl alcohol (PVA)/TiO2 composite polymer membrane was successfully synthesized at different TiO2 concentrations (20, 30, 40, and 50%) using the electro-spinning method. The parameters of electro-spinning including electrical field, tip-to-collector distance, and feed rate were optimized for fabrication process. The diameter of the electro-spun PVA-TiO2 fibers and average size of the TiO2 nano-particles loaded in the PVA nano-fibers ranged from 100 to 150 nm and 15 to 30 nm, respectively. X-ray diffraction analysis indicated that the main crystal structure was of the anatase type even though small rutile peaks were also observed for the PVA-TiO2 membrane. TiO2 nano-particles were embedded in the PVA fiber and were dispersed linearly along the fiber direction. As the amount of TiO2 loaded in PVA increased, the tensile strength also increased while the tensile strain significantly decreased. Also, when the TiO2 content was increased from 20 to 50%, the photocatalytic activity of the PVA-TiO2 membranes increased.